Research Article

Received: 18 November 2010 Accepted: 16 February 2011 Published online in Wiley Online Library: 31 March 2011

(wileyonlinelibrary.com) DOI 10.1002/jrs.2947

Raman study of pure, C-coated and Co-doped

LiFePO4: thermal effect and phase stability
upon laser heating
Ying Bai, Yanfeng Yin, Jueming Yang, Chunbo Qing and Weifeng Zhang∗
Pure, C-coated and Co-doped LiFePO4 were prepared by the hydrothermal method. X-ray diffraction patterns showed no
impurity phase after carbon coating and Co doping. Thermal effect and phase stability of the three samples as a function of
irradiation power density were systematically studied by means of Raman spectroscopy. The correlations between the power
density of the excitation laser and the surface structure were accurately established and compared. Results show that the
features of highest phase stability, excellent thermal stability and the most sensitive to power density were displayed in the
samples of pure, C-coated and Co-doped LiFePO4 , which were mainly ascribed to the grain size, thermal conductivity and degree
of order of the olivine structure, respectively. The results also indicate that particular attention should be paid in characterizing
the structure and component of the material surface by Raman spectroscopy, where the thermal effect of laser irradiation will
possibly alter material surface and thus induce wrong conclusions. Copyright
c 2011 John Wiley & Sons, Ltd.
Supporting information may be found in the online version of this article.

Keywords: thermal effect; phase stability; degree of order; LiFePO4 ; Raman spectroscopy

Introduction of detecting amorphous species, which may be missed out by X-ray

Olivine phase LiFePO4 has generated considerable interest
worldwide in past decade for its low cost and high stability. It
has a highly stable three-dimensional framework due to strong
P–O covalent bonds in the PO4 3− polyanion, which prevents
the liberation of oxygen[1] and keeps the stable framework
in the charge and discharge process.[2] This property provides
excellent safety and stable operation of Li batteries even under
unusual conditions.[3,4] However, the intrinsic low electronic
conductivity (10−9 S/cm[5] ) and slow diffusion of the Li ion (10−14
to 10−11 cm2 /s[6] ) of this material have severely hindered its
application in lithium ion batteries. Although there have been
numerous studies seeking to improve the cycling performance and
rate characteristic by carbon coating[7 – 9] and metal doping,[5,10 – 15]
there are few investigations on the differences of local structures of
the pure and modified LiFePO4 . Furthermore, the study of thermal
stabilities of the pure and modified materials and the possibility
to follow the evolutions of triphylite and iron oxides inside the
triphylite samples (it has been reported that magnetic clusters
are often present in triphylite-based materials[16] ) represent an
important goal in view of application purposes,[16,17] for which
it would be desirable to manage a system with stable and
reproducible functional parameters.
Raman spectroscopy is an excellent analytical technique for
probing the vibrational and structural properties of electrode
materials. This technique is especially useful for detecting
phosphate-based cathodes since the intramolecular vibrational
modes of the PO4 3− anions yield rich and intense bands in the
Raman spectrum, which are sensitive to the presence of Li+ ions.
Therefore, we believe with confidence that Raman spectroscopy
can provide us insight into the local structural and compositional
differences of the pure and modified LiFePO4 from the perspective
diffraction (XRD) or neutron diffraction techniques.
Co doping is beneficial for the electrochemical performances of
pure LiFePO4 , which was firstly confirmed by our experiments and
will be published elsewhere. It has been reported that the control
of LiFePO4 particle size is effective in increasing the charge and
discharge capacities.[3] Hydrothermal synthesis is a useful method
to prepare fine particles, with many advantages such as simple
synthesis process and low energy consumption.[18] Samples of
pure, C-coated and Co-doped LiFePO4 in the present paper were
prepared by the hydrothermal method. The obtained samples
were characterized by XRD and Raman spectroscopy. Although it
has been reported that the effectiveness of laser irradiation on the
phase stability of olivine and iron oxides can depend on different
factors like grain size,[13,16,19] thermal conductivity of the irradiated
region[16] and the degree of structural order,[16] the systematic
investigation and comparison of the thermal effect and phase
stabilities of the pure, C-coated and metal-doped LiFePO4 are rare,
and is a main feature of this work. It should be noted that as the
local temperature increases dramatically under confocal Raman
measurement, it was considered that the enhanced temperature,
namely thermal effect, was the intrinsic factor leading to changes
in the Raman spectra.
∗
Correspondence to: Weifeng Zhang, Key Laboratory of Photovoltaic Materials
ofHenan ProvinceandSchool ofPhysics&Electronics,Henan University,Kaifeng
475001, PR China. E-mail: wfzhang@henu.edu.cn; wfzhang6@163.com
Key Laboratory of Photovoltaic Materials of Henan Province and School of
831

of the PO4 3− anions. Moreover, Raman spectroscopy is also capable Physics & Electronics, Henan University, Kaifeng 475001, PR China

J. Raman Spectrosc. 2011, 42, 831–838 Copyright

c 2011 John Wiley & Sons, Ltd.
 Y. Bai et al.

Experimental
Sample preparation
Pure, C-coated and Co-doped LiFePO4 were synthesized by Co-doped LiFePO4
the hydrothermal method. LiOH·H2 O, FeSO4 · 7H2 O, H3 PO4 ,
Co(CH3 CO2 )2 · 4H2 O and sucrose were used as starting materials.

Counts
First, the starting materials were dissolved in deionized water C-coated LiFePO4
and mixed with vigorous stirring (for C-coated LiFePO4 , sucrose
was also added and for Co-doped sample, Co(CH3 CO2 )2 · 4H2 O
was added instead). In the precursor solution of C-coated and
Co-doped samples, the concentration of sucrose and Co2+ were pure LiFePO4
controlled to 7g/l and 0.5 mol/l, respectively. After homogeneous
mixing, the precursor solutions were quickly transferred to 0.1 l
stainless steel autoclaves and calcinated at 220 ◦ C for 2 h. Finally,
the products were filtered and dried. Parts of the freshly prepared 15 20 25 30 35 40 45 50 55 60 65
samples were compacted into pellets for Raman characterization. 2Theta/degrees

Figure 1. XRD patterns of pure, C-coated and Co-doped LiFePO4 .

Characterization methods
XRD (DX-2500, Fangyuan) measurement was performed on a
diffractometer with Cu Kα radiation with λ = 1.54145 Å. Scanning

Raman Intensity
electron microscopy (SEM, JSM-5600LV, JEOL) was used to
Co-doped LiFePO4
examine the morphologies of the three samples, where the
accelerating high voltage was 20 kV, the beam size 20 nm, the Raman Intensity C-coated LiFePO4

beam current 1 × 10−8 A and the vacuum condition 10−4 Pa. C-coated LiFePO4
pure LiFePO4
Raman investigations were conducted at room temperature on a
confocal micro-Raman spectrometer (Renishaw R-1000) equipped 850 900 950 1000
-1
Wavenumber/cm
with a charge-coupled device (CCD) detector. A 457.5 nm solid-
state laser was focused onto the surface of the powders through
a 50× microscope objective. The scattered light was collected Co-doped LiFePO4
in a backscattering geometry with spectral resolution of 1 cm−1 .
The laser irradiation power, which was determined by placing pure LiFePO4
a power meter on the sample stage, was about 1 mW and the
spot diameter of the laser beam was about 3.72 × 10−5 cm. 200 400 600 800 1000 1200 1400 1600
Neutral filters with different optical density values were used to Wavenumber/cm-1
irradiate the samples at different light intensities, giving power
density values from approximately 1 × 104 to 1 × 106 W/cm2 . Figure 2. Raman spectra of pure, C-coated and Co-doped LiFePO4 .
Each sample was measured under power densities in the order of The three curves were obtained using a moderate laser power of
2.5 × 105 W/cm2 at room temperature. In the inset, the symmetric
1 × 104 , 1 × 105 , 2.5 × 105 , 5 × 105 , 1 × 106 , 5 × 105 , 2.5 × 105 , stretching band of the samples is shown and compared, obtained under
1 × 105 and 1 × 104 W/cm2 . Under each power density, successive 1 × 104 W/cm2 .
measurements were conducted until a stable spectrum was
obtained. To obtain spectra with high signal-to-noise ratios, an
acquisition time of 5 min was set for a typical measurement. The Figure S1 (Supporting information) displays the SEM images
same region of a sample was exposed to varied power densities in of the as-prepared powders. The morphologies of pure and C-
the measurement process. coated LiFePO4 have similar features, showing dense stacked flaky
structures with edges and thickness of about 1.0 and 0.5 µm (Fig.
S1(a) and (b)). However, the morphology of Co-doped LiFePO4 is
totally different from those of pure and C-coated material, showing
Results and Discussion well-connected needle-like particles with an average particle size
Crystal structure and morphology of 300 nm (Fig. 3(c)). The markedly changed morphology of Co-
doped LiFePO4 provides strong evidence of Co doping in the
The XRD patterns of pure, C-coated and Co-doped LiFePO4 lattice structure of LiFePO4 . In other words, as shown in Fig. S1,
are shown in Fig. 1. All diffraction peaks are indexed to an carbon coating has less influence on the structure of LiFePO4
orthorhombic olivine structure (space group Pmnb) and no compared to Co doping, which corresponds with the XRD results
impurity phase was recorded within XRD detection limit after (Fig. 1).
C-coating and Co doping. Calculation with the Scherrer equation
showed that the grain sizes were 27.6, 28.0 and 24.7 nm for pure,
General Raman spectra
C-coated and Co-doped LiFePO4 , respectively. As the carbon
coating only influences the surface of the LiFePO4 particles, the Raman spectra of the three samples were collected under
grain size was almost unchanged. In contrast, a lower grain size moderate power density (2.5 × 105 W/cm2 ), as illustrated in
could be seen after Co doping, signifying the changes happened Fig. 2. Common features can be observed below 1200 cm−1 ,
832

in the bulk structure. which are the characteristic vibrations of LiFePO4 lattice (detailed

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c 2011 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2011, 42, 831–838
Raman study of pure, C-coated and Co-doped LiFePO4
pure LiFePO4
627
Agv4
Raman Intensity
571
Agv4 589
v4
444
v2
239 658
251 v4
289 324
195
157
200 400 600 800
Wavenumber/cm-1
Figure 3. Raman spectrum of pure LiFePO4 as-prepared and relative
assignments. The region below 700 cm−1 is scaled 10× so that the weak
bands may be more easily identified. The spectrum was obtained using a
moderate laser power of 2.5 × 105 W/cm2 at room temperature.
assignments are shown in Fig. 3). The broad peak near 1600 cm−1
for C-coated LiFePO4 is very well known and ascribable to the
presence of the graphitic carbon layer covering the triphylite
particles.[20] No evidence of impurity such as iron oxide was seen
in the Raman spectra, in accordance with the XRD results (Fig. 1).
A detailed comparison among the strongest Raman feature
allows us to define the difference in terms of the degree of order
through comparing the shape of symmetric stretching band near
950 cm−1 for the three samples, as shown in the inset of Fig. 2.
To exclude the influence of power density, the inset curves were
recorded under a low laser power of 1 × 104 W/cm2 . The pure
material demonstrates a sharp peak near 950 cm−1 , suggesting a
high degree of order. The fitting results give the widths (full-width
at half-maximum, FWHM) of 8.1274, 8.2785 and 9.9183 cm−1
for pure, C-coated and Co-doped LiFePO4 , respectively. It is
noteworthy that Co doping lowers the degree of order compared
to pure LiFePO4 , leading to a general deterioration of the Raman
scattering intensity with simultaneous line broadening. Previous
research has also indicated that the doping of Mn ions into
LiFePO4 will broaden the vibrational mode, tending to disturb the
vibrations of PO4 3− cages and lowering the degree of order.[13,16]
The intensity degradation of C-coated LiFePO4 is attributed to the
barrier layer of graphite that blocked off the signals from LiFePO4
to a certain extent in the measurement.
The nature and behavior of the vibrational modes for the
typical olivine structure have been widely studied and described
before.[13,15,21 – 25] The olivine structure belongs to spectroscopic
group D162h and the primitive cell is centrosymmetric with formula
units of PO4 3− . Li, Fe and P are distributed on octahedral 4a, 4c and
tetrahedral 4c sites (Wyckoff notation), respectively. The vibrational
bands of LiFePO4 can be divided into two classes: internal and
external optic modes.[26] The internal modes originate from the
intramolecular vibrations of the PO4 3− anion, are located above
400 cm−1 and are easy to assign. The external modes (lattice
vibrations), occurring below 400 cm−1 are composed primarily
of whole body translatory and librational motions of the PO4 3−
ions and translatory motion of the Fe2+ ions. Most of the external
modes are rather weak and cannot be assigned correctly without
the aid of calculation.[23]
J. Raman Spectrosc. 2011, 42, 831–838
950 The Raman features of pure LiFePO4 prepared by the hy-
Agv1
drothermal method are characterized in Fig. 3 (using a laser power
of 2.5 × 105 W/cm2 ). The modes in Fig. 3 agree very well with
the assignments reported in a previous report.[25] Four bands are
observed between 1100 and 900 cm−1 in the Raman spectrum
of pure LiFePO4 . The very sharp band with the highest intensity
near 950 cm−1 is attributed to the Ag symmetric P–O stretching
996 1067
vibration band of υ 1 , while the two weaker bands and a shoulder at
Agv3 A v 1081
g 3
high wavenumber between 990 and 1100 cm−1 are ascribed to the
B2gv3
antisymmetric stretching bands of the PO4 3− anion (υ 3 ). Theory
predicts υ 4 to yield six Raman vibrations (2Ag + B1g + 2B2g + B3g )
and υ 2 four Raman modes (Ag + B1g + B2g + B3g ) at the Brillouin
zone center.[26] Four bands between 550 and 700 cm−1 in Fig. 3 are
ascribed to υ 4 vibrations. A broad structure at ∼444 cm−1 could be
1000 1200 due to the overlapping of different bending modes of υ 2 . Referring
to the calculation results shown in a previous report,[25] the weak
features blow 400 cm−1 are strongly coupled. No assignment is
attempted for the low wavenumber Raman bands.
Thermal effect and phase stability upon laser heating
The effect of laser irradiation and thermal stability of pure LiFePO4
under different power densities was monitored by Raman spectra
and is shown in Fig. 4. The intensities of the vibrational peaks of
pure LiFePO4 increased distinctly as the power density increased
from 1 × 104 to 5 × 105 W/cm2 , as illustrated in Fig. 4(a). The
general features are similar among the four curves and no new
peak was observed. The main Raman mode of olivine cage, i.e.
the symmetric stretching vibration inside the PO4 3− units, near
950 cm−1 , experienced a red shift (see details in Fig. 7) and line
broadening as the power was increased. It has been reported
that the high-temperature Raman spectra often exhibit a red
shift of the bands and also an increase in band line width.[27,28]
Owing to the absorption of radiation in the confocal micro-Raman
arrangement, the local temperature might increase by hundreds of
degrees, contributing to a wavenumber shift and line broadening
of the Raman modes.
When the laser power reached 5 × 105 W/cm2 , five successive
measurements were conducted (Fig. 4(b)). Under laser irradiation,
the Raman spectra changed dramatically as time increased. In
the high-energy region, the characteristic band near 950 cm−1
was highly affected and depressed, demonstrating a red shift
(see details in Fig. 7) and line broadening, which implies that
the transformation induced by laser heating also provokes a
disordering of the molecular units of LiFePO4 . In the wavenumber
region below 400 cm−1 , the weak peaks belonging to LiFePO4
gradually vanished at the expense of two new peaks centered
at 215 and 277 cm−1 with increased intensities, which can be
assigned to α-Fe2 O3 .[16,23] Previous researchers have reported
that the magnetic clusters are often present in triphylite-based
materials,[16] and the thermal effect of irradiation can induce the
following transformation: Fe3 O4 → γ -Fe2 O3 → α-Fe2 O3 .[27] It
was considered that the small quantity of α-Fe2 O3 existing on the
particle surface was induced by laser irradiation at the local area.
The general changes got stabilized after continuous irradiation for
15 min.
When we made sure that the surface structure got stabilized
after irradiation under 5 × 105 W/cm2 (judging from the curves
in Fig. 4(b) and the peak center evolution near 950 cm−1 in
Fig. 7), the power density was further increased to 1 × 106 W/cm2 .
Significant changes took place under continuous irradiation, as
833
revealed in Fig. 4(c). The intensity of the LiFePO4 characteristic
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 Y. Bai et al.

Figure 4. Raman signals from pure LiFePO4 at different laser power levels: (a) monotonous increase of the laser power from 1×104 to 5×105 W/cm2 ; (b) five
successive measurements at 5 × 105 W/cm2 , each measurement time 5 min; (c) seven successive measurements at 1 × 106 W/cm2 , each measurement
time 5 min and (d) monotonous decrease of the laser power from 1 × 106 to 1 × 104 W/cm2 after continuous measurement at 1 × 106 W/cm2 for 35 min.

band near 950 cm−1 dropped rapidly, implying the breakdown
of the LiFePO4 crystal structure. The complex shape of the bands
between 900 and 1200 cm−1 is due to the presence of several
overlapping peaks on a broad background. In fact, it was difficult
to analyze and fit the asymmetric broad peaks in this region with
enough confidence (maybe each contained several distinct sharp
modes with different origins). The heavily affected and depressed
main Raman bands of the olivine cage under high laser power
level closely resembles what was recently observed in the study
of the Li insertion/extraction process in LiFePO4 /FePO4 .[16,29] A
topotactic two-phase process in which Li ions are removed from
the orthorhombic phase of LiFePO4 to form orthorhombic FePO4
is a general consensus among researchers.[1,30] A recent research
demonstrated that laser irradiation will destroy the FePO4 crystal
structure and form disordered FePO4 , with the band centered at
1003 cm−1 with large peak width.[22] Therefore, amorphous FePO4
induced by laser irradiation is believed to account for the high
and broad background near 1000 cm−1 . The new peaks near 216
and 278 cm−1 were attributed to α-Fe2 O3 clusters. No difference
can be observed among the seven lines in the low wavenumber
region, indicating that the transformation from Fe3 O4 to α-Fe2 O3
has been accomplished under 5 × 105 W/cm2 . After continuous
irradiation for 25 min under 1 × 106 W/cm2 , the surface structure
of the focal spot was stabilized (from Figs 4(c) and 7).
After stabilizing under 1 × 106 W/cm2 , the power density was
decreased gradually and the corresponding Raman spectra were
834
5 × 105 W/cm2 , four successive measurements were conducted
and no difference could be observed (not shown). Thus at lower
power densities, no repeat measurement was done. In comparison,
the stabilized curve under 1 × 106 W/cm2 is also shown in
Fig. 4(d). The mode near 950 cm−1 blue-shifted backward and
was accompanied by a narrowing of the band as the power
density decreased. Superficially, the intensity of the characteristic
peak near 950 cm−1 decreased as the power density dropped.
However, taking the lowered power density into account, the
actual intensity of this mode remained almost unchanged,
indicating that the structure of LiFePO4 was maintained to a
certain extent after high-power irradiation. The amorphous high
and broad background near 1000 cm−1 gradually disappeared
and distinct bands manifested at lower power densities. The
assignments of modes between 900 and 1200 cm−1 are marked
above the Raman curve measured under 2.5 × 105 W/cm2 in
Fig. 4(d). Bands belonging to olivine FePO4 , α-FePO4 and LiFePO4
can be observed, including several bands that could not be clearly
assigned so far. The Raman spectra of FePO4 have been intensively
studied by previous researchers.[22,23] Burba et al. found that
amorphous FePO4 formed through laser irradiation crystallized
in α-FePO4 when the laser was turned off.[22] Both olivine and
α-FePO4 were observed in the final products in Fig. 4(d),
suggesting the transformation from olivine to amorphous FePO4
was not complete under laser irradiation in this case. Considering
the decreased power densities, the new peaks centered at 216

recorded, as demonstrated in Fig. 4(d). With a laser power of and 278 cm−1 kept their intensities (Fig. 4(d)), suggesting α-Fe2 O3

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c 2011 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2011, 42, 831–838
Raman study of pure, C-coated and Co-doped LiFePO4
Figure 5. Raman signals from C-coated LiFePO4 at different laser power levels: (a) monotonous increase of the laser power from 1 × 104 to 1 × 106 W/cm2
and (b) monotonous decrease of the laser power from 1 × 106 to 1 × 104 W/cm2 .
clusters as part of the stable ultimate species at the surface of
LiFePO4 after laser irradiation.
A different behavior occurred for C-coated LiFePO4 , as can be
seen in Fig. 5, where the evolution of Raman spectra for this sample
under laser irradiation at different power densities was recorded.
The Raman curve of C-coated LiFePO4 kept fairly stable at each
distinct laser power, and no difference between two successive
measurements was shown under the same power density. Thus
only one curve is shown for a certain power density.
The intensities of the vibrational peaks of C-coated LiFePO4
enhanced markedly as the laser power increased from 1 × 104
to 5 × 105 W/cm2 (the bottom four curves in Fig. 5(a)). The
characteristic vibration near 950 cm−1 experienced a red shift
(see details in Fig. 7) and line broadening in this process, signifying
changes in the nature of this sample. When the laser power
increased from 5 × 105 to 1 × 106 W/cm2 (the top line in Fig. 5(a)),
dramatic changes could be observed. The complete loss of
intensity of the LiFePO4 bands indicated that the olivine crystal
structure was completely destroyed when the power density
reached 1 × 106 W/cm2 . Although the exact thermal conductivity
of C-coated LiFePO4 is still unknown, the Raman spectra in Fig. 5(a)
show that the sample is able to dissipate the thermal energy
and strain accumulated from the laser irradiation even when the
power density reaches 5 × 105 W/cm2 . Under a higher power
density, 1 × 106 W/cm2 , however, the rate at which the thermal
energy and lattice strain is released is surpassed by that at which
energy and strain are deposited into the sample by the laser
irradiation. As a result, new peaks in the 900–1300 cm−1 region
and below 300 cm−1 appeared. A high and broad background
between 900 and 1300 cm−1 existed in the Raman curve under
1 × 106 W/cm2 , as shown by the top line of Fig. 5(a)), which is
the same curve and is more clearly presented in the top line of
Fig. 5(b). The broad background at 1000 cm−1 here was ascribed
to disordered FePO4 . In low wavenumber region, new modes
emerged at 215 and 277 cm−1 , which can be assigned to α-Fe2 O3 .
As the laser power was decreased (Fig. 5(b)), the background at
1000 cm−1 was depressed and closely resembled to the behavior
of pure LiFePO4 (Fig. 4(d)), suggesting the disappearance of
amorphous FePO4 . However, different from that of pure LiFePO4 ,
the symmetric stretching band of PO4 3− near 950 cm−1 was
absent under 1 × 106 W/cm2 and never recovered as the power
density decreased, implying the disordering and irreversibility of
the olivine LiFePO4 structure. The assignments of peaks between
900 and 1400 cm−1 are labeled above the Raman curve obtained
J. Raman Spectrosc. 2011, 42, 831–838 Copyright

c 2011 John Wiley & Sons, Ltd.
under 2.5 × 105 W/cm2 (in Fig. 5(b)). Both olivine FePO4 and
α-FePO4 were observed in the ultimate products, indicating that
the transformation from olivine to amorphous FePO4 was not
complete. Taking the decreased laser powers into account, the
new peaks centered at 216 and 278 cm−1 kept their intensities
(Fig. 5(b)), suggesting a stable finite product of α-Fe2 O3 clusters.
It is obvious that the formation of hematite clusters and
disordering of LiFePO4 structure were delayed for C-coated
LiFePO4 (Fig. 5(a)) compared to the pure material (Fig. 4(b)). On
the other hand, the C-coated LiFePO4 got stabilized much faster
under each power density. Even when the power density reached
1 × 106 W/cm2 , the structure seemed to be stabilizing in a very
short time. This feature is very different with that of pure LiFePO4 ,
of which the structure often needed a longer period to become
stabilized. As can be seen in Fig. 2, only graphite carbon existed on
the surface of C-coated LiFePO4 , which is in favor of heat transfer.
It has been reported that lattice strain wis the driving force for
the nucleation of α-Fe2 O3 clusters.[27] Under laser irradiation, less
heat and lattice strain will be accumulated in C-coated LiFePO4
compared to the pure material, although the grain size and degree
of order of the two samples are quite close.
The Raman spectra of Co-doped LiFePO4 were collected as a
function of laser power, as presented in Fig. 6. The intensities
of vibrational peaks of Co-doped LiFePO4 increased obviously as
the power density increased from 1 × 104 to 2.5 × 105 W/cm2 ,
as shown in the bottom three curves in Fig. 6(a). No new peak
is found in these curves. The characteristic peak near 950 cm−1
experienced red shift (Fig. 7) and line broadening in this process,
indicating a lowered degree of order. When the laser power
was increased from 2.5 × 105 to 5 × 105 W/cm2 (the top line in
Fig. 6(a)), great changes were found. In the high wavenumber
region, considering the enhanced power density, the band near
950 cm−1 quickly lost its intensity concurrently with broadening,
indicating fast disordering of the LiFePO4 crystal. Simultaneously,
in the low energy region, new peaks appeared near 211 and
279 cm−1 , which can be assigned to α-Fe2 O3 clusters under the
thermal effect of laser irradiation.
Four successive measurements were carried out under the laser
power of 5 × 105 W/cm2 (Fig. 6(b)). It took the surface structure
only 10 min to get stabilized under this power density. Under
continuous laser irradiation, new peaks centered at 216 and
278 cm−1 got stronger intensities at the expense of the mode
near 950 cm−1 which lost most of its intensity within 10 min,
835
demonstrating the formation of α-Fe2 O3 clusters and disordering
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 Y. Bai et al.

Figure 6. Raman signals from Co-doped LiFePO4 at different laser power levels: (a) monotonous increase of the power density from 1 × 104 to
5 × 105 W/cm2 ; (b) four successive measurements at 5 × 105 W/cm2 , each measure time 5 min; (c) three successive measurements at 1 × 106 W/cm2 , each
measure time 5 min and (d) monotonous decrease of the power density from 1 × 106 to 1 × 104 W/cm2 after continuous measurement at 1 × 106 W/cm2
for 20 min.

950.0 before, the broad background near 1000 cm−1 was ascribed to
pure LiFePO4 disordered FePO4 under laser irradiation. No difference could
C-coated LiFePO4 be found under three successive measurements in the general
Peak center near 950cm-1/cm-1

949.6 Co-doped LiFePO4

1*104 W/cm2 wavenumber region, signifying the quick stabilization achieved
1*104 W/cm2
1*10 W/cm2
5 for this material.
2.5*104 W/cm2 2.5*104 W/cm2 The Raman curves when the laser decreased are presented in
5 2
949.2 1*10 W/cm
Fig. 6(d). Assignments of the peaks between 900 and 1400 cm−1
5*105 W/cm2
5*105 W/cm2
are marked above the Raman curve measured under 2.5 ×
105 W/cm2 . No band near 950 cm−1 can be found, indicating the
948.8
irreversibility of olivine LiFePO4 structure at the local spot. Both
olivine FePO4 and α-FePO4 can be observed in the final products,
1*106 W/cm2 implying that the transformation from olivine to amorphous FePO4
948.4
was not complete. Two low wavenumber peaks belonging to
-2 0 2 4 6 8 10 12 14 16 18 20 α-Fe2 O3 clusters remained unchanged considering the decreased
Measure Sequence power densities, suggesting a stable final product of α-Fe2 O3 .
As reported by previous researchers, the ability to accommodate
Figure 7. Evolution of the vibrational peak centered near 950 cm−1 for the stress is better for small particles than for large grains.[27] The grain
three samples.
size of Co-doped LiFePO4 is smaller than that of the pure material,
which explains the faster stabilization of the general spectra under
laser irradiation.
of LiFePO4 in this period. After 10 min, the Raman curves showed
no difference with the previous one, indicating stabilization of the
Band shift and shape change upon laser heating
surface structure.
When the power density increased to 1 × 106 W/cm2 (Fig. 6(c)), Laser-irradiation-induced shift of the phonon band near 950 cm−1
the mode near 950 cm−1 was completely absent. Instead, two for the three samples are evaluated and compared in Fig. 7. For
strong, broad bands with high and broad background near clarity, some vertical broken lines have been added to separate the
836

1000 cm−1 appeared in the high wavenumber region. As stated measurements under varied power densities. As a representative

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c 2011 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2011, 42, 831–838
Raman study of pure, C-coated and Co-doped LiFePO4
of LiFePO4 vibrations, this band showed a red shift and broadening
(Fig. S2, Supporting information) as the laser power increased for
the three samples. Pure and C-coated LiFePO4 demonstrated a
mild shift rate compared to Co-doped material, demonstrating the
influence of grain size. The smaller the grain size, the faster seems
to be the red shift for the symmetric mode of PO4 3− . Referred to the
analogous phenomena in the Raman spectra of porous silicon[31]
and the analysis of the temperature dependence of Raman red
shift,[32] phonon confinement as well as bond expansion and bond
weakening were considered to account for the red shift and line
broadening, which will be more prominent for fine-sized materials.
The characteristic band completely vanished for C-coated and
Co-doped LiFePO4 under high-power density, and never recovered
as the laser power was decreased. However, it showed reversibility
in pure LiFePO4 : when the laser power was decreased, this
mode blue-shifted backward gradually (Fig. 7), demonstrating the
reversibility of the LiFePO4 structure after laser irradiation, which
can be attributed to the large grain size and high degree of order
of this sample.
Comparison and analysis
The power density of 5 ×105 W/cm2 is sufficient to induce damage
of the LiFePO4 crystal for pure and Co-doped LiFePO4 ; however,
it enhanced until 1 × 106 W/cm2 when the LiFePO4 feature was
damaged severely. In another aspect, as described before, the
formation of α-Fe2 O3 clusters appeared to be the latest for
C-coated LiFePO4 (1 × 106 W/cm2 ). Generally speaking, under
laser irradiation, the C-coated material showed the fastest stability
rate and the strongest thermal endurance, which were ascribed
to the high thermal conductivity after carbon coating. With high
thermal conductivity, it is not easy to accumulate heat and lattice
strain. For this reason, it is understandable that the spectral change
happened rather late and quickly.
For Co-doped material, the change happened at the power
density of 5 × 105 W/cm2 , both in the formation of hematite and
the degradation of olivine LiFePO4 . Additionally, the stabilization
of surface structure seemed to be more easily compared to that
of pure LiFePO4 under the same power irradiation. The most
sensitive characteristic to power density of Co-doped LiFePO4 can
be attributed to its small grain size and low degree of order.
Examination under a microscope showed that the local spots
of the three samples subjected to laser irradiation exhibited dis-
tinctive brown-red features, which are characteristic of hematite.
As part of the final products, hematite was formed during differ-
ent periods for the three samples (Figs 4–6), which resulted from
the oxidation of magnetite under laser heating. Shebanova et al.
believed that for small grains, the oxidation rate from Fe3 O4 to
α-Fe2 O3 is sufficiently high even at low temperatures, whereas
higher temperatures are required if the grains are larger.[27] The
difference in behavior depending on the grain size can be ex-
plained by the lattice strain developing during oxidation, as has
been advanced by Gallagher et al.[33] ; the ability to accommodate
stress is better for smaller grains than for larger ones. Obviously,
Co-doped sample has the smallest grain size, accounting for its
fastest formation of α-Fe2 O3 than pure LiFePO4 . On the other hand,
because of the high thermal conductivity of C-coated LiFePO4 , it is
not easy for the accumulation of heat and lattice strain, which ex-
plains that the formation of α-Fe2 O3 happened only at high-power
densities compared to the pure sample.
J. Raman Spectrosc. 2011, 42, 831–838 Copyright

c 2011 John Wiley & Sons, Ltd.
Implication in Raman measurement
Raman spectroscopy is more sensitive to the material surface
compared to XRD. Although Raman spectroscopy can provide
many valuable insights into the local structure and component
of electrodes used in lithium ion batteries, particular attention
should be paid to the high-energy laser. Besides Lix MPO4 and
MPO4 (M = Fe, Ni, Mn and Co), other electrode materials also
demonstrate sensitivity to laser power. Song et al.[34] and Fu
et al.[35] reported significant changes in LiCoO2 -based samples
upon exposure to laser beam, and laser-induced decomposition
of spinel LiMn2 O4 has been observed by Paolone et al.[36] Bai and
co-workers recorded the great changes of the vibrational bands
of silicon, and the decoupled modes were also detected at high
laser powers.[28] Shebanova et al. found phase change of Fe3 O4
under laser irradiation, and established the correlations between
the excitation laser power, the temperature of the sample spot
and the degree of oxidation of magnetite.[27] Generally speaking,
owing to the absorption of radiation in the confocal micro-
Raman setup, the local temperature may increase by hundreds of
degrees, inducing the wavenumber shift of Raman modes, or even
the sample alteration as the result of oxidation, recrystallization,
order–disorder transitions, phase transition or decomposition.[27]
The present experimental results strongly suggest that the power
setting of the excitation laser should be carefully controlled in
Raman spectroscopy measurements.
Conclusions
The Raman spectra of pure, C-coated and Co-doped LiFePO4 as
a function of laser power density were reported and compared
for the first time. Though there still remained several peaks that
cannot be assigned so far after high-power-density irradiation, the
thermal effect and phase stability of the three samples are clear.
It can be concluded that the effectiveness of laser irradiation
especially depends on the grain size, thermal conductivity and
degree of order of the olivine structure: the more ordered the
structure, the larger the grain size and the lower the thermal
conductivity, the less effective the transformation. The most stable
of olivine phase lies in pure LiFePO4, which showed reversibility to a
certain extent, wherein the large grain size and high degree of order
were thought to account for this feature. C-coated LiFePO4 showed
the highest thermal stability and strongest thermal endurance,
which was attributed to the enhanced thermal conductivity after
the high-graphite carbon coating. Co-doped material was the most
sensitive to power density, representing both in the formation of
hematite and the degradation of olivine LiFePO4 , and the small
grain size and low degree of order was believed to account for the
results.
Hematite phase was observed in the ultimate product of the
three samples, which could be ascribed to the transformation
from magnetite under thermal effect and lattice strain of laser
irradiation. FePO4 structure was considered to experience the
phase transformation of olivine FePO4 →amorphous FePO4 → α-
FePO4 in the power increase and decrease process.
Special care should be paid in Raman characterization of
materials, particularly for micro-Raman experiments where the
laser beam is focused on a spot with a diameter of only a few
micrometers, which can substantially change the local crystal
structure or even decompose the local area, leading to wrong
conclusions. It is highly beneficial to refer to previous studies
837
and/or calculation results before the measurement. If neither of
wileyonlinelibrary.com/journal/jrs

them can be consulted, however, the fitting results of the Raman
spectra both under low- and high-power densities should be
compared. The line under high-power density cannot be accepted
if the difference lies not only in band intensity and signal-to-noise
ratio.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (50902044 and 60976016), the Project
of Cultivating Innovative Talents for Colleges and Universities
of Henan Province (2002006), the project of Henan Province
Department of Education (2010B480004) and Natural Science
Foundation of Henan University (2008YBZR018).
Supporting information
Supporting information may be found in the online version of this
article.
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